CN101118932A - Conductive slurry for front electrode of solar battery - Google Patents
Conductive slurry for front electrode of solar battery Download PDFInfo
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- CN101118932A CN101118932A CNA2007100455346A CN200710045534A CN101118932A CN 101118932 A CN101118932 A CN 101118932A CN A2007100455346 A CNA2007100455346 A CN A2007100455346A CN 200710045534 A CN200710045534 A CN 200710045534A CN 101118932 A CN101118932 A CN 101118932A
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Abstract
The present invention relates to a conductive paste for the front surface of the solar energy battery,l comprising an electric phase metal powder, a glass phase and an organic phase; the present invention is provided with zero point zero five to one percent additive on base of the total weight of the conductive paste; the additive is TiO2 powder or SnO2 powder. The front electrode of the solar energy battery adopts the conductive paste, so the present invention not only enhances the peeling mechanical intensity of the front electrode of the battery, but also enhances the filling factor FF of the battery, reduces the resistance in series and enhances the light conversion efficiency; and the present invention makes the battery have a good balance of the synthesis electric capability and the mechanical capability.
Description
Technical field
This clam relates to conductive slurry for front electrode of solar battery.
Background technology
In solar cell making process, need at its n
+Form an Ohm contact electrode on the N-type semiconductor N.The method that forms Ohm contact electrode has two kinds, and the one, adopt vacuum vapour deposition, the 2nd, adopt silk screen print method.In order to reduce the production cost of solar cell, realize industrialization and large-scale production, generally adopt method for printing screen.
It is to adopt thick film conductor paste that method for printing screen prepares front electrode of solar battery, is coated on the silicon chip, and through super-dry, sintering in infrared sintering furnace makes it metallization and forms electrode then.
The electrocondution slurry that silk screen printing is used has conductive phase, glassy phase and organic carrier phase composition.Conductive phase mainly is made up of silver powder, as the conductive materials of electrode.Glassy phase mainly produces liquefaction in sintering process, cohering of silicon chip and electrode is provided.Organic carrier provides suitable viscosity and thixotropy mutually, makes it to have good printing performance.
Conventional solar cell is by p
-Type substrate, n
+Front phosphorus emitter, (typically subtracting transmitting film is Si to be printed on metal electrode, antireflective coating above the passivation layer
3N
4), aluminium back side contact and p
+The aluminium back of the body (BSF) is formed.In battery manufacturing process during the electrode metal sintering, glassy phase offers following silicon substrate contact in surface and coheres in the electrocondution slurry.The ohmic contact that forms is etching SiN fully
xAntireflective coating.When temperature during greater than 600 ℃, glassy phase begins liquid stateization, wetting silicon nitride antireflective coating, and begin to dissolve silver-colored particle at its contact surface.Along with the rising of temperature, glassy phase begins silicon nitride film, until all penetrate silicon nitride film, the silicon emitter surface begins to be dissolved in the glassy phase.In addition, glassy phase is as the medium of silver-colored transfer of granules to the silicon emitter surface, and in sintering process, silver-colored particle recrystallization is on the silicon emitter surface.It is exactly dissolving and the recrystallization of silver-colored particle by glassy phase that the screen printing electrode metallization forms ohmic contact.Glassy phase content hour can not form well between silicon chip and electrode and cohere in electrocondution slurry, and the stripping machine intensity of electrode reduces.If glassy phase content increases in the electrocondution slurry, softening in sintering process and flowing, between silicon face and electrode, form an insulating barrier, cause the increase of contact resistance, therefore the value volume and range of product of glassy phase is the principal element of decision contact resistance, silicon face etching, open circuit voltage Voc and fill factor, curve factor FF in the electrocondution slurry, and it has determined also whether battery has the good electrical property and the balance of mechanical performance.
In the evolution of the manufacturing of solar cell, all be round the photoelectric conversion efficiency that improves solar cell and reduce these two emphasis of production cost of solar cell.By reducing contact resistance is to improve one of phototranstormation efficiency effective ways.
In WO2003025945,, in slurry, add the Fe of 0.1-10wt% by reducing the content of glassy phase in the electrocondution slurry
2O
3, FeO, MnO, Cu
2This quasi-metal oxides of O both reached and can reduce contact resistance, can have the purpose of the stripping electrode mechanical strength that satisfies application requirements again.But this type oxide in sintering process and glass react, make the viscosity of glass diminish, be easy between silicon face and electrode, form one deck glass dielectric layer, cause the series resistance of battery to increase, fill factor, curve factor reduces, thereby cell conversion efficiency reduces.
Summary of the invention
The purpose of this invention is to provide a kind of conductive slurry for front electrode of solar battery, to overcome the above-mentioned defective that prior art exists.
Electrocondution slurry of the present invention comprises conductive phase metal dust, glassy phase and organic facies, based on the total weight of electrocondution slurry, also contains the additive of 0.05-1wt%, and said additive is TiO
2Powder or SnO
2Powder, preferably TiO
2Powder, preferred content is 0.1-0.5wt%;
Said additive agent powder granular size should be similar to the conductive phase metal dust.If addition is less than 0.05wt%, it is big that contact resistance becomes, and fill factor, curve factor diminishes; And when addition during greater than 1wt%, the stripping electrode mechanical strength reduces.Therefore, 0.1-0.5wt% preferably;
Preferably, the component of electrocondution slurry of the present invention and weight percent content comprise:
Conductive phase metal dust 60-90%,
Glassy phase 1-10%
Organic facies 8-25%
Additive 0.05-1%
Said conductive metal powder is a silver powder, and the granular size scope is 0.1-10 μ m, and form is sphere or torispherical, if silver powder particles is greater than 10 μ m, electrode silver powder dissolution velocity in sintering process is slow, and the amount minimizing at silicon face recrystallization silver causes contact resistance to increase; And when silver powder particles during less than 0.1 μ m, itself being easy to sintering in the electrode sintering process shrinks, and cracks between electrode and the silicon face, makes degradation of cell performance.Therefore, the silver powder particles size is preferably 2-6 μ m;
Said glassy phase is a Si-B-Al-Pb-O system glass, and softening temperature is 440 ℃-560 ℃, and electrode is at 600 ℃ of-900 ℃ of following sintering.When the softening temperature of glassy phase during less than 440 ℃, in the electrode sintering process, the glassy phase condensing temperature is low, and liquid longer duration burns emitter.And when softening temperature during, the bond strength that can not obtain greater than 560 ℃; If glassy phase content is less than 1wt%, the electrode bond strength reduces.And when greater than 10wt%, not only the electrical property of battery descends, and the solderability of electrode also will be by deterioration, preferably 3-6wt%;
Said Si-B-Al-Pb-O system glass can adopt traditional melting method to be prepared;
Said organic facies is made up of solvent and tackifier.Solvent is terpinol, butyl carbitol, butyl carbitol acetate or citrate etc., and tackifier are ethyl cellulose, butyl cellulose, nitrocellulose etc.; Solvent: tackifier are 40: 1～5: 1 (wt/wt), and the organic facies addition is 8-25wt%;
With above-mentioned four component premixeds in container, on three-roller, mix then and roll, measuring fineness with Hegman grind gage is 10-15 μ m, measuring viscosity with viscosity apparatus is 100-300Pa.s (BrookfieldHBT/10rpm, 25 ℃), promptly obtain silk screen printing with the front electrode of solar battery slurry.
The present invention adds TiO in electrocondution slurry
2Or SnO
2, TiO
2And SnO
2In sintering process, do not change the wetting and etching of glassy phase to antireflective coating, and the dissolving of silver-colored particle in glassy phase.In cooling procedure, because TiO
2, SnO
2Play the effect of nucleus agent in glass, make to produce crystallite at silicon mutually with the electrode interface upper glass, because the glassy phase controlled micro crystallization, dissolving silver degree of supersaturation in glassy phase increases, and the crystallization silver quantity of separating out increases, and contact resistance diminishes.Simultaneously, increased conductive contact points and tunnel effect, made resistance decreasing because the controlled micro crystallization of glassy phase provides more interface.The crystallite of glassy phase produces one " pinning " effect at silicon face, thereby makes bond strength increase.Can satisfy the stripping machine intensity of electrode, have low series resistance and high fill factor, curve factor again.
Therefore, conductive slurry for front electrode of solar battery of the present invention not only makes battery just and the stripping machine intensity of electrode improves, and the fill factor, curve factor FF of battery increases, series resistance reduces, and phototranstormation efficiency improves, and makes battery have the good comprehensive electrochemical properties and the balance of mechanical performance.
Embodiment
Embodiment 1
With silver powder (average grain diameter is 2.5 μ m) 80.7g, glass powder 3.0g, (terpinol: ethyl cellulose is 10 to organic facies: 1wt/wt) be 16g, TiO
2Be 0.3g premixed in blender, on three-roller, mix then and roll, obtain electrocondution slurry.Make the front electrode of solar cell with this slurry by silk screen printing, be prepared into solar cell according to a conventional method, measure its fill factor, curve factor FF, series resistance Rs, transformation efficiency η and stripping electrode intensity, its result is as shown in table 1.
The definition and the detection method of fill factor, curve factor FF, series resistance Rs, transformation efficiency η and stripping electrode intensity have detailed description and report in the disclosed document of relevant solar cell.
Embodiment 2-4 and comparative example 1-3
Electrocondution slurry preparation technology and battery preparation technique be similar in appearance to embodiment 1 in embodiment 2-4 and comparative example 1-3, except changing the content of silver powder and glassy phase, and different additives and addition, its form and the battery performance result as shown in table 1.
Table 1 electrocondution slurry is formed and solar cell properties
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Silver powder/g | 80.7 | 80.7 | 79.2 | 79.2 | 80.2 | 79.2 | 81.0 |
| Glassy phase/g | 3.0 | 3.0 | 4.6 | 4.2 | 3.8 | 4.8 | 3.0 |
| Organic facies/g | 16 | 16 | 16 | 16 | 16 | 16 | 16 |
| TiO 2/g | 0.3 | 0 | 0.2 | 0.6 | 0 | 0 | 0 |
| SnO 2/g | 0 | 0.3 | 0 | 0 | 0 | 0 | 0 |
| FF | 1.026 | 1.022 | 1.028 | 1.020 | 1 | 0.93 | 0.96 |
| Rs | 0.752 | 0.812 | 0.763 | 0.850 | 1 | 1.07 | 1.05 |
| η | 1.031 | 1.025 | 1.030 | 1.012 | 1 | 0.95 | 0.97 |
| Adhesion strength | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Relatively poor |
Fill factor, curve factor FF, series resistance Rs, phototranstormation efficiency η with comparative example are 1, and other compares relative value with it.
Claims (10)
1. conductive slurry for front electrode of solar battery is characterized in that, comprises conductive phase metal dust, glassy phase and organic facies, based on the total weight of electrocondution slurry, also contains the additive of 0.05-1wt%, and said additive is TiO
2Powder or SnO
2Powder.
2. conductive slurry for front electrode of solar battery according to claim 1 is characterized in that, additive is TiO
2Powder.
3. conductive slurry for front electrode of solar battery according to claim 1 is characterized in that, content of additive is 0.1-0.5wt%.
4. conductive slurry for front electrode of solar battery according to claim 2 is characterized in that, content of additive is 0.1-0.5wt%.
5. conductive slurry for front electrode of solar battery according to claim 1 is characterized in that, the component and the weight percent content of said electrocondution slurry comprise:
Conductive phase argent powder 60-90%,
Glassy phase 1-10%
Organic facies 8-25%
Additive 0.05-1%.
6. conductive slurry for front electrode of solar battery according to claim 1 is characterized in that, said conductive metal powder is a silver powder, and the granular size scope is 0.1-10 μ m, and form is sphere or torispherical.
7. conductive slurry for front electrode of solar battery according to claim 1 is characterized in that, said glassy phase is a Si-B-Al-Pb-O system glass.
8. conductive slurry for front electrode of solar battery according to claim 7 is characterized in that, the glassy phase softening temperature is 440 ℃-560 ℃.
9. conductive slurry for front electrode of solar battery according to claim 1, it is characterized in that, said organic facies is made up of solvent and tackifier, solvent is terpinol, butyl carbitol, butyl carbitol acetate or citrate, and tackifier are ethyl cellulose, butyl cellulose or nitrocellulose.
10. conductive slurry for front electrode of solar battery according to claim 9 is characterized in that solvent: tackifier are 40: 1～5: 1 (wt/wt).
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|---|---|---|---|
| CNA2007100455346A CN101118932A (en) | 2007-09-03 | 2007-09-03 | Conductive slurry for front electrode of solar battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100455346A CN101118932A (en) | 2007-09-03 | 2007-09-03 | Conductive slurry for front electrode of solar battery |
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| CN101118932A true CN101118932A (en) | 2008-02-06 |
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ID=39054942
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| CNA2007100455346A Pending CN101118932A (en) | 2007-09-03 | 2007-09-03 | Conductive slurry for front electrode of solar battery |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163649A (en) * | 2010-12-29 | 2011-08-24 | 友达光电股份有限公司 | Method for manufacturing solar cell |
| CN101630695B (en) * | 2009-08-05 | 2011-11-02 | 贵研铂业股份有限公司 | Lead-free cadmium-free electrode slurry for crystalline silicon solar battery and preparation method thereof |
| CN102280161A (en) * | 2011-08-18 | 2011-12-14 | 陈晓东 | Conductive paste for positive electrode of crystal silicon solar cell and preparation method of conductive paste |
| CN102368390A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Low temperature solidification conduction slurry and preparation method thereof |
| CN102368388A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Conductive slurry and preparation method thereof |
| CN102368392A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Low cost conductive slurry and preparation method thereof |
| CN102368396A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Multi-component conductive paste and preparation method thereof |
| CN102368395A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Novel polyester conductive slurry material and preparation method thereof |
| CN102368394A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Environment-friendly electroconductive slurry and preparation method thereof |
| CN102368393A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Solar electroconductive slurry and preparation method thereof |
| CN102368389A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Conductive organic slurry and preparation method thereof |
| CN102651247A (en) * | 2011-02-25 | 2012-08-29 | 苏州晶银新材料股份有限公司 | Novel conductive sizing agent for front-electrode of solar photovoltaic cell |
| CN102803171A (en) * | 2009-06-17 | 2012-11-28 | 旭硝子株式会社 | Glass frit for formation of electrode, and electrically conductive paste for formation of electrode and solar cell each utilizing same |
| CN103021510A (en) * | 2011-09-22 | 2013-04-03 | 比亚迪股份有限公司 | Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste |
| CN104205243A (en) * | 2012-03-23 | 2014-12-10 | 株式会社昌星 | Electrode paste composition for solar cell |
| CN106251934A (en) * | 2016-09-27 | 2016-12-21 | 北京市合众创能光电技术有限公司 | Hyperfine electronic printing slurry |
| CN107611186A (en) * | 2017-10-21 | 2018-01-19 | 长沙仲善新能源科技有限公司 | Crystal silicon solar energy battery positive conductive silver paste and preparation method thereof |
| CN113299422A (en) * | 2021-05-07 | 2021-08-24 | 江西师范大学 | Crystalline silicon solar cell front silver paste and preparation method thereof |
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2007
- 2007-09-03 CN CNA2007100455346A patent/CN101118932A/en active Pending
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| CN102803171A (en) * | 2009-06-17 | 2012-11-28 | 旭硝子株式会社 | Glass frit for formation of electrode, and electrically conductive paste for formation of electrode and solar cell each utilizing same |
| CN101630695B (en) * | 2009-08-05 | 2011-11-02 | 贵研铂业股份有限公司 | Lead-free cadmium-free electrode slurry for crystalline silicon solar battery and preparation method thereof |
| CN102163649A (en) * | 2010-12-29 | 2011-08-24 | 友达光电股份有限公司 | Method for manufacturing solar cell |
| CN102651247A (en) * | 2011-02-25 | 2012-08-29 | 苏州晶银新材料股份有限公司 | Novel conductive sizing agent for front-electrode of solar photovoltaic cell |
| CN102651247B (en) * | 2011-02-25 | 2013-06-19 | 苏州晶银新材料股份有限公司 | Novel conductive sizing agent for front-electrode of solar photovoltaic cell |
| CN102280161B (en) * | 2011-08-18 | 2013-08-28 | 陈晓东 | Conductive paste for positive electrode of crystal silicon solar cell and preparation method of conductive paste |
| CN102280161A (en) * | 2011-08-18 | 2011-12-14 | 陈晓东 | Conductive paste for positive electrode of crystal silicon solar cell and preparation method of conductive paste |
| CN102368389A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Conductive organic slurry and preparation method thereof |
| CN102368388A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Conductive slurry and preparation method thereof |
| CN102368389B (en) * | 2011-08-31 | 2013-02-27 | 安徽祈艾特电子科技有限公司 | Conductive organic slurry and preparation method thereof |
| CN102368390A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Low temperature solidification conduction slurry and preparation method thereof |
| CN102368392A (en) * | 2011-08-31 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Low cost conductive slurry and preparation method thereof |
| CN102368393A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Solar electroconductive slurry and preparation method thereof |
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| CN102368394A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Environment-friendly electroconductive slurry and preparation method thereof |
| CN102368396A (en) * | 2011-09-01 | 2012-03-07 | 安徽祈艾特电子科技有限公司 | Multi-component conductive paste and preparation method thereof |
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| CN102368395B (en) * | 2011-09-01 | 2013-02-27 | 安徽祈艾特电子科技有限公司 | Novel polyester conductive slurry material and preparation method thereof |
| CN103021510A (en) * | 2011-09-22 | 2013-04-03 | 比亚迪股份有限公司 | Front electrode silver paste of crystalline silicon solar battery and preparation method for front electrode silver paste |
| CN103021510B (en) * | 2011-09-22 | 2016-04-13 | 比亚迪股份有限公司 | A kind of crystal silicon solar energy battery front electrode silver slurry and preparation method thereof |
| CN104205243A (en) * | 2012-03-23 | 2014-12-10 | 株式会社昌星 | Electrode paste composition for solar cell |
| CN106251934A (en) * | 2016-09-27 | 2016-12-21 | 北京市合众创能光电技术有限公司 | Hyperfine electronic printing slurry |
| CN107611186A (en) * | 2017-10-21 | 2018-01-19 | 长沙仲善新能源科技有限公司 | Crystal silicon solar energy battery positive conductive silver paste and preparation method thereof |
| CN107611186B (en) * | 2017-10-21 | 2019-07-09 | 山西森达源科技集团有限公司 | Crystal silicon solar energy battery positive conductive silver paste and preparation method thereof |
| CN113299422A (en) * | 2021-05-07 | 2021-08-24 | 江西师范大学 | Crystalline silicon solar cell front silver paste and preparation method thereof |
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Open date: 20080206 |